Adv Polym Sci (2014) 255: 139–172
DOI: 10.1007/12_2012_178
# Springer-Verlag Berlin Heidelberg 2012
Published online: 16 September 2013
Relaxation Phenomena During Polyelectrolyte
Complex Formation
Saskia Lindhoud and Martien A. Cohen Stuart
Abstract Polyelectrolyte complex formation is a well-studied subject in colloid
science. Several types of complex formation have been studied, including PEMs,
macroscopic polyelectrolyte complexes, soluble complexes and polyelectrolyte
complex micelles. The chemical nature of the complex-forming polyelectrolytes
and the environmental conditions (e.g., pH, ionic strength and temperature) influence the final structural properties of these complexes. This chapter deals with the
kinetics of polyelectrolyte complex formation and discusses how ionic strength,
charge density and pH influence the dynamics of the complexes, which can range
from glass-like (solid) precipitates to liquid-like phases. The switching between the
glass-like and liquid-like phase as a function of the ionic strength has a strong
analogy to the phase behaviour of polymer melts as function of temperature.
By performing calorimetry during complex formation it has been found that the
enthalpy of complex formation of systems that form glass-like phases has an
opposite sign to the enthalpy of systems that form liquid-like phases, i.e., the
formation of glass-like phases is exothermic and the formation of liquid-like phases
is endothermic. The free energy (D f G), enthalpy (D f H) and entropy (D f S) of
polyelectrolyte complex formation and how they vary as a function of the ionic
strength will be discussed.
Results from dynamic light scattering (DLS) titrations, Atomic Force Microscopy (AFM), surface force measurements and rheology will be used to illustrate
how differences in kinetics show up in experiments on colloidal micellar systems.
S. Lindhoud (*) and M.A. Cohen Stuart
Laboratory of Physical Chemistry and Colloid Science, Wageningen University,
Dreijenplein 6, 6703 HB Wageningen, The Netherlands
e-mail: saskia.lindhoud@gmail.com; martien.cohenstuart@wur.nl
DOI: 10.1007/12_2012_178
# Springer-Verlag Berlin Heidelberg 2012
Published online: 16 September 2013
Relaxation Phenomena During Polyelectrolyte
Complex Formation
Saskia Lindhoud and Martien A. Cohen Stuart
Abstract Polyelectrolyte complex formation is a well-studied subject in colloid
science. Several types of complex formation have been studied, including PEMs,
macroscopic polyelectrolyte complexes, soluble complexes and polyelectrolyte
complex micelles. The chemical nature of the complex-forming polyelectrolytes
and the environmental conditions (e.g., pH, ionic strength and temperature) influence the final structural properties of these complexes. This chapter deals with the
kinetics of polyelectrolyte complex formation and discusses how ionic strength,
charge density and pH influence the dynamics of the complexes, which can range
from glass-like (solid) precipitates to liquid-like phases. The switching between the
glass-like and liquid-like phase as a function of the ionic strength has a strong
analogy to the phase behaviour of polymer melts as function of temperature.
By performing calorimetry during complex formation it has been found that the
enthalpy of complex formation of systems that form glass-like phases has an
opposite sign to the enthalpy of systems that form liquid-like phases, i.e., the
formation of glass-like phases is exothermic and the formation of liquid-like phases
is endothermic. The free energy (D f G), enthalpy (D f H) and entropy (D f S) of
polyelectrolyte complex formation and how they vary as a function of the ionic
strength will be discussed.
Results from dynamic light scattering (DLS) titrations, Atomic Force Microscopy (AFM), surface force measurements and rheology will be used to illustrate
how differences in kinetics show up in experiments on colloidal micellar systems.
S. Lindhoud (*) and M.A. Cohen Stuart
Laboratory of Physical Chemistry and Colloid Science, Wageningen University,
Dreijenplein 6, 6703 HB Wageningen, The Netherlands
e-mail: saskia.lindhoud@gmail.com; martien.cohenstuart@wur.nl